Diketopyrrolopyrrole oligomers for use in organic semiconductor devices

ABSTRACT

The present invention relates to oligomers of the formula (I), and their use as organic semiconductor in organic devices, especially in organic photovoltaics (solar cells) and photodiodes, or in a device containing a diode and/or an organic field effect transistor. High efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the oligomers according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

The present invention relates to 1,4-diketopyrrolo[3,4-c]pyrrole (DPP)derivatives of formula I, to their manufacture; and to their use asorganic semiconductors, e.g. in semiconductor devices, especially asensor, a diode, a photodiode, an organic field effect transistor, atransistor for flexible displays, and/or a solar cell (photovoltaiccell).

Examples of DPP polymers and their synthesis are, for example, describedin US6451459B1, WO05/049695, WO2008/000664, EP2034537A2, EP2075274A1,WO2010/049321, WO2010/049323, WO2010/108873, WO2010/115767,WO2010/136353, WO2010/136352 and WO2011/144566 (PCT/EP2011/057878).

Matthias Horn et al., Eur. Polymer J. 38 (2002) 2197-2205 describes thesynthesis and characterisation of thermomesogenic polysiloxanes with2,5-dihydropyrrolo[3,4-c]pyrrole units in the main chain.

M. Smet et al., Tetrahedron Letters 42 (2001) 6257-6530 describesoligomers, which are prepared by a stepwise sequence of suzuki couplingsusing brominated 1,4-dioxo-3,6-diphenylpyrrolo[3,4c]pyrrole (DPPderivatives) and 1,4-dibromo-2,5-di-n-hexylbenzene as the monomers. Theresulting oligomers contained three, five and seven DPP units,respectively.

WO2003048268 relates to an organic electroluminescent device comprisinga perylene derivative and a diketopyrrolopyrrole derivative, such as,for example,

WO06/061343 discloses fluorescent diketopyrrolopyrroles of the formula

wherein R¹ and R² may be the same or different and are selected from aC₁-C₂₅alkyl group, an allyl group, which can be substituted one to threetimes with C₁-C₃alkyl, a cycloalkyl group, which can optionally besubstituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, acycloalkyl group, which is condensed one or two times by phenyl whichcan be substituted one to three times with C₁-C₄-alkyl, halogen, nitro,or cyano, an alkenyl group, a cycloalkenyl group, an alkynyl group, aheterocyclic group, haloalkyl, haloalkenyl, haloalkynyl, a heterocyclicgroup, a ketone or aldehyde group, an ester group, a carbamoyl group, asilyl group, a siloxanyl group, aryl, heteroaryl, or —CR³R⁴—(CH₂)_(m)-A³wherein R³ and R⁴ independently from each other stand for hydrogen orC₁-C₄alkyl, or phenyl which can be substituted one to three times withC₁-C₃alkyl, A³ stands for aryl, or heteroaryl, in particular phenyl or1- or 2-naphthyl, which can be substituted one to three times withC₁-C₈alkyl and/or C₁-C₈alkoxy, and m stands for 0, 1, 2, 3 or 4, A⁴ andA⁵ independently of each other stands for

wherein R¹⁰¹ to R¹²³ may be the same or different and are selected fromhydrogen, C₁-C₂₅alkyl group, cycloalkyl, aralkyl, alkenyl, cycloalkenyl,alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ethergroup, an aryl thioether group, aryl, a heterocyclic group, halogen,haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, acarbonyl group, a carboxyl group, an ester group, a carbamoyl group, agroup NR²⁷R²⁸, wherein R²⁷ and R²⁸ are as defined above, a nitro group,a silyl group, a siloxanyl group, a substituted or unsubstituted vinylgroup, or at least two adjacent substituents R¹¹⁵ to R¹²¹ form anaromatic, heteroaromatic or aliphatic fused ring system,R¹²⁴ and R¹²⁵ may be the same or different and are selected fromC₁-C₁₈alkyl; C₁-C₁₈alkoxy, A³, C₆-C₁₈aryl; C₇-C₁₈aralkyl; or R¹²⁴ andR¹²⁵ together form a ring especially a five-, six- or seven-memberedring, which can optionally be substituted by C₁-C₈alkyl, or which canoptionally be condensed one or two times by phenyl which can besubstituted one to three times with C₁-C₈-alkyl, C₁-C₈-alkoxy, halogenand cyano; or a heteroaromatic group, especially

wherein R¹³¹ to R¹⁵² may be the same or different and are selected fromhydrogen, C₁-C₂₅alkyl group, cycloalkyl, aralkyl, alkenyl, cycloalkenyl,alkynyl, hydroxyl, a mercapto group, alkoxy, alkylthio, an aryl ethergroup, an aryl thioether group, aryl, a heterocyclic group, halogen,haloalkyl, haloalkenyl, haloalkynyl, a cyano group, an aldehyde group, acarbonyl group, a carboxyl group, an ester group, a carbamoyl group, agroup NR²⁷R²⁸, wherein R²⁷ and R²⁸ are as defined above, a nitro group,a silyl group, a siloxanyl group, a substituted or unsubstituted vinylgroup, R¹⁵³ is a hydrogen atom, a C₁-C₂₅alkyl group, which might beinterrupted by —O—, a cycloalkyl group, an aralkyl group, an aryl group,or a heterocyclic group, and A⁶ is cycloalkyl, arylene, orheteroarylene, which are optionally substituted one to three times withC₁-C₈-alkyl, or C₁-C₈-alkoxy; and their use for the preparation of inks,colorants, pigmented plastics for coatings, non-impact-printingmaterial, color filters, cosmetics, polymeric ink particles, toners, asfluorescent tracers, in color changing media, in solid dye lasers, ELlasers and electroluminescent devices.

The following compounds are explicitly mentioned in WO06/061343:

Cpd. A⁴ = A⁵ A⁶ R¹ = R² D-1

CH₃ D-2

CH₃ D-3

CH₃ D-4

CH₃ D-5

CH₃ D-6

CH₃ D-7

CH₃

JP2006310538 discloses fluorescent diketopyrrolopyrroles of the formula

wherein Ar⁶ may be aryl, or heteroryl, and its use in light emittingelements.

WO2007/003520 relates to fluorescent compounds, such as, for example,

a process for their prepn. and their use for the prepn. of inks,colorants, pigmented plastics for coatings, non-impact-printingmaterial, color12 filters, cosmetics, polymeric ink particles, toners,as fluorescent tracers, in color changing media, dye lasers andelectroluminescent devices.

US2010/0326525 relates to optoelectronic devices, such as photovoltaicdevices, comprising:

a) a first hole-collecting electrode;

b) an optional hole-transporting layer;

c) a layer comprising a mixture of an electron donor material and anelectron acceptor material; and

d) a second electron-collecting electrode,

wherein the electron donor material comprises a compound of Formula (I):

wherein X is oxygen or sulfur;A₁ and A₂ are independently selected from substituted and unsubstitutedaryl or heteroaryl groups, wherein each individual A₁ within the (A₁)mmoiety can be independently selected from a substituted or unsubstitutedaryl or heteroaryl group, and each individual A₂ within the (A₂)n moietycan be independently selected from a substituted or unsubstituted arylor heteroaryl group;B₁ is independently selected from substituted and unsubstituted aryl orheteroaryl groups;m is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9;n is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9;p is independently selected from 0 or 1;E₁ and E₂ are independently selected from a nonentity, H, or asubstituted or unsubstituted aryl or heteroaryl group or a C₁-C₁₂ alkylgroup; andR₁, R₂, R₃, and R₄ are independently selected from H, C₁-C₁₂ alkyl, and—C(—O)—O—C₁-C₁₂ alkyl.

The following dimeric DPP compound is explicitly disclosed:

Y. Xu et al., Synthetic Metals 160 (2010) 2135-2142 reports thesynthesis of DPP-containing oligomers:

The monomers were copolymerized with benzothiadiazole, dioctyloxybenzeneand fluorene through fluoride-mediated Suzuki polymerization to givecopolymers with low content of DPP (1 mol %). The copolymers were usedas the emitting layers in the light-emitting diodes.

R. A. J. Janssen et al., Macromol. Chem. Phys. 2011, 212, 515-520disclose diketopyrrolopyrrole-based oligomers of formula

(R=2-hexyldecyl; n=1 to 4), which were prepared nickel (0)-mediatedYamamoto coupling reaction of a mixture of mono- and dibrominatedmonomers

Monodisperse oligomers were obtained from the resulting mixture byseparation of the oligomers using recycling GPC. Their optical andelectrochemical properties were investigated. For all properties,measured in solution, no clear change was observed upon increase of thechain length, leading to the conclusion that conjugation in this systemis only very limited.

Stephen Loser et al., J. Am. Chem. Soc., DOI:10.1021/ja202791n•Publication Date (Web): 5 May 2011 describes thesynthesis, characterization, and first implementation of anaphtho[2,3-b:6,7-b′]dithiophene (NDT)-based donor molecule in highlyefficient organic photovoltaics (OPVs). When NDT(TDPP)₂(TDPP=thiophene-capped diketopyrrolopyrrole:

R=2-ethylhexyl)) is combined with the electron acceptor PC61BM, a powerconversion efficiency (PCE) of 4.06±0.06% is achieved.

Yuning Li et al., J. Mater. Chem. 21 (2011) 10829 [published on web: 9Jun. 2011] discloses the synthesis of the following polymer

(R=2-octyldodecyl) and its use in OFETs.

C. H. Woo et al., J. Am. Chem. Soc. 132 (2010) 15547 [published on web:14 Oct. 2010] discloses the synthesis of the following polymers

R=2-ethylhexyl,X═S, Y═S; X═O, Y═S; or X═O, Y═O; and its use in solar cells.

R. A. J. Janssen et al., J. Mater. Chem. 21 (2011) 1600 [published onweb: 6 Dec. 2010] discloses the synthesis of the following polymers

R=2-hexyldecyl, X═O, Y═S; X═O, Y═O; or X═S, Y═O; and its use in OFETsand solar cells.

EP2033983A2 is directed to DPP polymers having a structure representedby:

wherein each X is independently selected from S, Se, O, and NR″, each R″is independently selected from hydrogen, an optionally substitutedhydrocarbon, and a hetero-containing group, each Z is independently oneof an optionally substituted hydrocarbon, a hetero-containing group, anda halogen, d is a number which is at least 1, e is a number from zero to2; a represents a number that is at least 1; b represents a number from0 to 20; each M is an optional, conjugated moiety and n represents anumber that is at least 1.

Among others the following polymers are disclosed:

wherein n is the number of repeat units and can be from about 2 to about5000, R′″, R″″ and R′″″ can be the same or different substituent, andwherein the substituent is independently selected from the groupconsisting of an optionally substituted hydrocarbon group and aheteroatom-containing group. For n is 2 no end group is defined.

WO2011025454A1 discloses compounds of formula

and its use in electronic devices. X is O, S or Se. D can be amongothers

Among others the following polymers are disclosed:

wherein n is 2 to 15000. For n is 2 no end group is defined.

It is the object of the present invention to provide compounds, whichshow high efficiency of energy conversion, excellent field-effectmobility, good on/off current ratios and/or excellent stability, whenused in organic field effect transistors, organic photovoltaics (solarcells) and photodiodes.

It has surprisingly been found that certain dimeric, trimeric andquatermeric diketo-pyrrolopyrrol derivatives can be used as organicsemiconductors. Said derivatives have excellent solubility innon-halogenated organic solvents (allowing easy handling). They can besynthesized easier than polymers (allowing cost savings), and they areeasy to purify (allowing very pure products to be obtained at low cost).

Accordingly, the present invention relates to compounds of the formula

whereinp is 0, or 1, q is 0, or 1,A¹ and A² are independently of each other a group of formula

A³, A⁴ and A⁵ are independently of each other a group of formula

a is 1 or 2; b is 0, 1 or 2; c is 0, 1 or 2;k is 0, 1, or 2; l is 1, 2, or 3; r is 0, or 1; z is 0, 1 or 2;R¹, R², R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) and R^(2*) may be thesame or different and are selected from hydrogen, a C₁-C₁₀₀alkyl groupwhich can optionally be substituted one or more times with C₁-C₁₂alkyl,C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group or a siloxanyl group and/orcan optionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO— or —OCO—,a C₂-C₁₀₀ alkenyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group or asiloxanyl group and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, —COO—, —CO— or —OCO—,a C₃-C₁₀₀alkinyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group or asiloxanyl group and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, —COO—, —CO— or —OCO—,a C₃-C₁₂cycloalkyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group or asiloxanyl group and/or can optionally be interrupted by —O—, —S—,—NR³⁹—, —COO—, —CO— or —OCO—,a C₆-C₂₄aryl group which can optionally be substituted one or more timeswith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano,vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group or a siloxanylgroup,a C₂-C₂₀heteroaryl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro,cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group or asiloxanyl group,—CO—C₁-C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl, —COO—C₁-C₁₈alkyl;R³ is hydrogen, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which issubstituted one or more times by E and/or interrupted one or more timesby D,

COO—C₁-C₁₈alkyl, a C₄-C₁₈cycloalkyl group, a C₄-C₁₈ cycloalkyl group,which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl,C₁-C₁₈thioalkoxy, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, C₇-C₂₅aralkyl, or C₇-C₂₅aralkyl, which issubstituted by G, or a

Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are independently of each other abivalent group of formula

X is —O—, —S—, —NR¹⁰—, —Si(R¹⁸)(R¹⁹)—, —Ge(R¹⁸)(R¹⁹)—, —C(R¹²)(R¹³)—,—C(═O)—, —C(═CR¹⁴R¹⁵)—,

R¹⁰ and R¹¹ are independently of each other hydrogen, C₁-C₁₈alkyl,C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl,R¹² and R¹³ are independently of each other hydrogen, C₁-C₁₈alkyl,C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, or 2-C₂₀heteroaryl, or R¹²and R¹³ together represent oxo,

or form a five or six membered ring, which is unsubstituted orsubstituted by C₁-C₁₈alkyl and/or C₁-C₁₈alkoxy;R¹⁴ and R¹⁵ are independently of each other hydrogen, C₁-C₁₈alkyl,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, —CN or COOR⁵⁰;R¹⁶ and R¹⁷ are independently of each other hydrogen, halogen,C₁-C₂₅alkyl, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

R^(x) is a C₁-C₁₂alkyl group, or a tri(C₁-C₈alkyl)silyl group,R¹⁸ and R¹⁹ are independently of each other hydrogen, C₁-C₁₈alkyl,C₇-C₂₅arylalkyl, or a phenyl group, which optionally can be substitutedone to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy,R²⁰ and R²¹ are independently of each other hydrogen, C₁-C₂₅alkyl,C₂-C₂₅alkenyl, C₂-C₂₅alkyl which is interrupted by one or more —O— or—S—, COOR⁵⁰, cyano, C₁-C₁₈ alkoxy, C₆-C₂₄aryl, C₇-C₂₅arylalkyl, halogenor C₂-C₂₀heteroaryl, or R²⁰ and R²¹ together represent alkylene oralkenylene which may be both bonded via oxygen and/or sulfur to the(hetero)aromatic residue and which may both have up to 4 carbon atoms,R³⁰ to R³⁷ are independently of each other hydrogen, C₁-C₂₅alkyl,C₂-C₂₅alkenyl, C₂-C₂₅alkyl which is interrupted by one or more —O— or—S—, COOR⁵⁰, cyano, C₁-C₂₅alkoxy, C₆-C₂₄aryl, C₇-C₂₅arylalkyl, halogenor C₂-C₂₀heteroaryl,R⁴⁰ and R⁴¹ are independently of each other hydrogen, C₁-C₂₅alkyl,C₂-C₂₅alkenyl, C₂-C₂₅alkyl which is interrupted by one or more —O— or—S—, COOR⁵⁰, cyano, C₁-C₁₈alkoxy, C₆-C₂₄aryl, C₇-C₂₅arylalkyl, halogenor C₂-C₂₀heteroaryl,R⁵⁰ is C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₇-C₂₅arylalkyl, C₆-C₂₄aryl orC₂-C₂₀heteroaryl;R⁶⁰ to R⁶⁸ represent independently of each other H, halogen, cyano,C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, a C₄-C₁₈cycloalkyl group, aC₄-C₁₈ cycloalkyl group, which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, C₇-C₂₅aralkyl, or C₇-C₂₅aralkyl, which issubstituted by G,R⁷⁰ and R⁷¹ are independently of each other hydrogen, C₁-C₂₅alkyl, orC₇-C₂₅aralkyl, or R⁷⁰ and R⁷¹ together represent alkylene or alkenylenewhich may be both bonded via oxygen and/or sulfur to the thienyl residueand which may both have up to 25 carbon atoms,D is —CO—, —COO—, —S—, —O—, —NR³⁹—, or —C(═O)NR³⁹—,E is C₁-C₈thioalkoxy, COO—C₁-C₁₈alkyl, C₁-C₈alkoxy, CN, —NR³⁹R^(39′),—CONR³⁹R^(39′), or halogen,G is E, or C₁-C₁₈alkyl,R³⁹ and R^(39′) are independently of each other hydrogen, C₁-C₁₈alkyl,C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl,with the proviso that at least one of the groups Ar¹, Ar², Ar³, Ar⁴,Ar⁵, Ar⁶ and Ar⁷ is a group of formula:

and the further proviso that Ar⁵ is different from a group

if q is 0, p is 0, k is 0, r is 0, z is 0 and l is 1.

The molecules of formula (I) consist preferably of a mirror-symmetricalsequence of building blocks selected from Ar¹ to Ar⁷ and thediketopyrrolopyrrole basic skeletons.

The compound of formula I is preferably a compound of formula

wherein A¹, A², A³, A⁴, A⁵, R¹, R², R^(1′), R^(2′), R^(1″), R^(2″),R^(1*) and R^(2*) are as defined above.

At least one Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ and Ar⁷ is a group

Preferably at least one of Ar¹, Ar⁴ and Ar⁷ is a group.

More preferably Ar¹ is

Most preferably Ar¹, Ar⁴ and Ar⁷ are a group

If Ar¹, Ar⁴ or Ar⁷ is a furan ring, the furan ring is preferablymono-substituted (position away from the DPP)

or not substituted, most preferably not substituted

R¹, R², R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) and R^(2*) may be thesame or different and are preferably selected from hydrogen, aC₁-C₁₀₀alkyl group which can optionally be substituted one or more timeswith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano, C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or can optionally be interrupted by —O—, —S—,—COO— or —OCO—,

a C₂-C₁₀₀alkenyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or can optionally be interrupted by—O—, —S—, —COO— or —OCO—,

a C₃-C₁₀₀alkinyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or can optionally be interrupted by—O—, —S—, —COO— or —OCO—,

a C₄-C₁₂cycloalkyl group which can optionally be substituted one or moretimes with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl and/or can optionally be interrupted by—O—, —S—, —COO— or —OCO—,

a C₆-C₂₄aryl group which can optionally be substituted one or more timeswith C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a C₂-C₂₀heteroaryl group which canoptionally be substituted one or more times with C₁-C₁₂alkyl,C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, —CO—C₁-C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl, and—COO—C₁-C₁₈alkyl.

More preferably R¹, R², R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) andR^(2*) are selected from hydrogen, C₁-C₅₀alkyl, C₁-C₅₀haloalkyl,C₇-C₂₅arylalkyl, C₂-C₅₀alkenyl, C₂-C₅₀haloalkenyl, allyl,C₅-C₁₂cycloalkyl, phenyl, or naphthyl which can optionally besubstituted one or more times with C₁-C₁₂alkyl or C₁-C₁₂alkoxy,—CO—C₁-C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl and —COO—C₁-C₁₈alkyl. Even morepreferably R¹, R², R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) and R^(2*) area C₁-C₅₀₀alkyl group. Still more preferably R¹, R², R^(1′), R^(2′),R^(1″), R^(2″), R^(1*) and R^(2*) are a C₁-C₃₆alkyl group. Mostpreferably R¹, R², R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) and R^(2*) area C₁₂-C₂₄alkyl group, very especially a C₁₆-C₂₄alkyl group. PreferablyR¹ is R², R^(1′) is R^(2′), R^(1″) is R^(2″) and R^(1*) is R^(2*). Mostpreferably R¹, R², R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) and R^(2*)have the same meaning.

Advantageously, the groups R¹, R², R^(1′), R^(2′), R^(1″), R^(2″),R^(1*) and R^(2*) can be represented by formula

wherein m1=n1+2 and m1+n1≦24. Chiral side chains, such as R¹, R²,R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) and R^(2*), can either behomochiral, or racemic, which can influence the morphology of thecompounds.

Preferably a is 1; b is 0, 1, or 2; c is 0, 1, or 2; more preferably ais 1; b is 0, or 1, c is 0, or 1; still more preferably a is 1; b is 0,or 1; c is 0; most preferably a is 1; b is 0; c is 0.

Preferably k+l+r+z is an integer smaller than 5; more preferably k+l+r+zis an integer from 1 to 4; even more preferably k+l+r+z is an integerfrom 1 to 3; most preferably k+l+r+z is 1 or 3. If q is 0, p is 0, k is0, r is 0, z is 0 and l is 1, Ar⁵ is preferably different from a group

In a preferred embodiment of the present invention two furan groups arenot linked directly by a single bond.

Preferably A¹ and A² are the same in the compounds of formulas (Ia),(Ib) and (Ic). Preferably A³ and A⁴ are the same in the compound offormula (Ib). Preferably A³ and A⁵ are the same in the compound offormula (Ic). More preferably A³, A⁴ and A⁵ are the same in the compoundof formula (Ic).

A¹ and A² are independently of each other a group of formula

whereina is 1, b is 0, or 1, c is 0, or 1,Ar¹, Ar² and Ar³ are independently of each other a group of formula

R¹⁰ is hydrogen, C₁-C₂₅alkyl or COO—C₁-C₂₅alkyl,R¹⁶ and R¹⁷ are independently of each other hydrogen, halogen,C₁-C₂₅alkyl, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

R^(x) is a C₁-C₁₂alkyl group, or a tri(C₁-C₈alkyl)silyl group,R²⁰ and R²¹ are independently of each other hydrogen, or C₁-C₂₅alkyl,R³⁰ to R³⁵ are independently of each other hydrogen, or C₁-C₂₅alkyl,R⁴² and R⁴³ are independently of each other C₁-C₂₅alkyl;R³ is hydrogen, halogen, cyano, C₁-C₂₅ alkyl, or a group of formula

whereinR⁶⁰ to R⁶⁸ represent independently of each other hydrogen orC₁-C₂₅alkyl;R⁷⁰ and R⁷¹ are independently of each other hydrogen, or C₁-C₂₅alkyl, orR⁷⁰ and R⁷¹ together represent alkylene which may be both bonded viaoxygen and/or sulfur to the thienyl residue and which may both have upto 25 carbon atoms.

Preferably, R⁷⁰ and R⁷¹ are independently of each other hydrogen, orC₁-C₂₅alkyl.

In a preferred embodiment of the present invention A¹ and A² areindependently of each other a group of formula,

whereina is 1, b is 0, or 1, c is 0, or 1,

Ar² and Ar³ are independently of each other

and R³ is H, C₁-C₂₅alkyl, or phenyl.

In a preferred embodiment of the present invention A³, A⁴ and A⁵ areindependently of each other a group of formula

k is 0, 1, or 2; l is 1, 2, or 3; r is 0, or 1; z is 0, 1 or 2;Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are independently of each other a group of formula

R¹⁰ is hydrogen, C₁-C₂₅alkyl or COO—C₁-C₂₅alkyl,R¹⁶ and R¹⁷ are independently of each other hydrogen, halogen,C₁-C₂₅alkyl, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

R^(x) is a C₁-C₁₂alkyl group, or a tri(C₁-C₈alkyl)silyl group,R²⁰ and R²¹ are independently of each other hydrogen, or C₁-C₂₅alkyl,R³⁰ to R³⁵ are independently of each other hydrogen, or C₁-C₂₅alkyl, andR⁴² and R⁴³ are independently of each other C₁-C₂₅alkyl.

More preferably, A³, A⁴ and A⁵ are independently of each other a groupof formula

k and z are 0, or 1; l is 1, 2, or 3; r is 0;Ar⁴ and Ar⁷ are a group of formula

Ar⁵ is a group of formula

y is 1, 2, or 3,R¹⁰ is H, or C₁-C₂₅alkyl,R¹⁶ and R¹⁷ are H, or C₁-C₂₅alkyl, andR³² and R³³ are H, or C₁-C₂₅alkoxy.

Preferably R³ is hydrogen, halogen, cyano, C₁-C₂₅ alkyl, or a group offormula

More preferably R³ is hydrogen, halogen, cyano, C₁-C₂₅ alkyl or

Still more preferably R³ is hydrogen, or C₁-C₂₅ alkyl. Most preferablyR³ is hydrogen.

Preferably Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are independently ofeach other a bivalent group of formula

Ar¹, Ar⁴ and Ar⁷ are preferably selected in such a manner, so that nosix-membered ring is directly attached to the diketopyrrolopyrrole basisskeleton.

More preferably Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are independentlyof each other a bivalent group of formula

Ar¹, Ar⁴ and Ar⁷ are preferably selected in such a manner, so that nosix-membered ring is directly attached to the diketopyrrolopyrrole basisskeleton.

Even more preferably Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ and Ar⁷ areindependently of each other a group of formula

Ar¹, Ar⁴ and Ar⁷ are preferably selected in such a manner, so that nosix-membered ring is directly attached to the diketopyrrolopyrrole basisskeleton.

If two moieties selected from Ar¹ to Ar⁷ are linked via a single bond,preferably less than 4 substituents in ortho position to this linkingbond selected from R¹⁴, R¹⁵, R²⁰, R²¹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, R³⁸, R⁴⁰, R⁴¹ are not hydrogen. More preferably less than 3substituents in ortho position to this linking bond selected from R¹⁴,R¹⁵, R²⁰, R²¹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R⁴⁰, R⁴¹ arenot hydrogen. Even more preferably only one substituent in orthoposition to this linking bond selected from R¹⁴, R¹⁵, R²⁰, R²¹, R³⁰,R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R⁴⁰, R⁴¹ is not hydrogen. Mostpreferably all substituents in ortho position to this linking bondselected from R¹⁴, R¹⁵, R²⁰, R²¹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶,R³⁷, R³⁸, R⁴⁰, R⁴¹ are hydrogen.

If a moiety selected from Ar¹, Ar⁴ or Ar⁷ is linked via a single bond tothe DPP basis skeleton, preferably the substituents in ortho position tothis linking bond selected from R¹⁴, R¹⁵, R²⁰, R²¹, R³⁰, R³¹, R³², R³³,R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R⁴⁰, R⁴¹ are hydrogen.

In a preferred embodiment of the present invention A¹ and A² areindependently of each other a group of formula

A³, A⁴ and A⁵ are independently of each other a group of formula

wherein k is 1, I is 1, z is 1, and r is 0,Ar¹, Ar⁴, and Ar⁷ are

Ar², Ar³, Ar⁵, Ar⁶ are independently of each other a group of formula

Ar¹, Ar⁴ and Ar⁷ are preferably selected in such a manner, so that nosix-membered ring is directly attached to the diketopyrrolopyrrole basisskeleton.

Preferably X is —O—, —S—, —NR¹⁰—, —Si(R¹⁸)(R¹⁹)—, —C(R¹²)(R¹³)—,

More preferably X is —O—, —S—, —NR¹⁰—, —C(R¹²)(R¹³)—,

Most preferably X is —S—, —NR¹⁰—, or

R¹⁰ and R¹¹ are independently of each other hydrogen, C₁-C₁₈alkyl,C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl, preferablyhydrogen, C₁-C₁₈alkyl, C₁-C₁₈ alkanoyl; most preferably C₁-C₁₈alkyl.

Preferably R¹² and R¹³ are independently of each other hydrogen,C₁-C₁₈alkyl, C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, or R¹² and R¹³ togetherrepresent oxo, or

More preferably R¹² and R¹³ are independently of each other hydrogen,C₁-C₁₈ alkyl, or R¹² and R¹³ together represent oxo. Most preferably R¹²and R¹³ are independently of each other C₁-C₁₈alkyl.

R¹⁴ and R¹⁵ are independently of each other hydrogen, C₁-C₁₈ alkyl,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, —CN or COOR⁵⁰. Preferably R¹⁴ and R¹⁵ areindependently of each other hydrogen, C₁-C₁₈ alkyl, —CN, or COOR⁵⁰,where more preferably at least one of R¹⁴ and R¹⁵ is —CN, or COOR⁵⁰, andespecially R¹⁴ and R¹⁵ are both —CN.

R¹⁶ and R¹⁷ are independently of each other hydrogen, halogen,C₁-C₂₅alkyl, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

R^(x) is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group.

Preferably R¹⁸ and R¹⁹ are C₁-C₁₈ alkyl.

Preferably R²⁰ and R²¹, are independently of each other hydrogen,C₁-C₂₅alkyl, COOR⁵⁰, cyano, C₁-C₁₈alkoxy, or halogen. More preferablyR²⁰ and R²¹, are independently of each other hydrogen, C₁-C₂₅alkyl,C₁-C₁₈ alkoxy, or halogen. Even more preferably R²⁰ and R²¹ areindependently of each other hydrogen, or C₁-C₂₅alkyl. Most preferablyR²⁰ and R²¹ are hydrogen;

Preferably R³⁰ to R³⁷ are independently of each other hydrogen,C₁-C₂₅alkyl, COOR⁵⁰, cyano, C₁-C₁₈alkoxy, or halogen. More preferablyR³⁰ to R³⁸ are independently of each other hydrogen, C₁-C₂₅alkyl, C₁-C₁₈alkoxy, or halogen. Even more preferably R³⁰ to R³⁸ are independently ofeach other hydrogen or C₁-C₂₅alkyl. Most preferably R³⁰ to R³⁸ arehydrogen.

Preferably R⁴⁰ and R⁴¹ are independently of each other hydrogen,C₁-C₂₅alkyl, COOR⁵⁰, or cyano. More preferably R⁴⁰ and R⁴¹, areindependently of each other hydrogen, C₁-C₂₅alkyl, or cyano. Even morepreferably R⁴⁰ and R⁴¹ are independently of each other hydrogen, orC₁-C₂₅alkyl. Most preferably R⁴⁰ and R⁴¹ are independently of each otherC₁-C₂₅alkyl.

Preferably R⁴² and R⁴³ are independently of each other C₁-C₁₈ alkyl.

R⁵⁰ is C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, orC₂-C₂₀heteroaryl. R⁵⁰ is preferably C₁-C₂₅alkyl, C₁-C₂₅haloalkyl,C₇-C₂₅arylalkyl, most preferably C₁-C₂₅alkyl.

Preferably R⁶⁰ to R⁶⁸ represent independently of each other hydrogen,C₁-C₂₅alkyl, C₁-C₁₈ alkoxy, or halogen. More preferably R⁶⁰ to R⁶⁸represent independently of each other hydrogen, or C₁-C₂₅alkyl. Mostpreferably R⁶⁰ to R⁶⁸ represent hydrogen.

In a particularly preferred embodiment the present invention is directedto compounds of formula

Even more preferred are compounds of formula

In another particularly preferred embodiment the present invention isdirected to compounds of formula

Even more preferred are compounds of formula

b is 0, or 1, c is 0, or 1.

A³, A⁴, Ar⁵ and Ar⁶ are independently of each other a group of formula

y is 1, 2, or 3.

Ar² and Ar³ are independently of each other

R³ is H, C₁-C₂₅alkyl, or phenyl. R¹⁰ is H, or C₁-C₂₅alkyl. R¹⁶ and R¹⁷are H, or C₁-C₂₅alkyl. R³² and R³³ are H, or C₁-C₂₅alkoxy.

R¹, R², R^(1′), R^(2′), R^(1*) and R^(2*) are selected from hydrogen,C₁-C₅₀alkyl, C₁-C₅₀haloalkyl, C₇-C₂₅arylalkyl, C₂-C₅₀alkenyl,C₂-C₅₀haloalkenyl, allyl, C₅-C₁₂cycloalkyl, phenyl, or naphthyl whichcan optionally be substituted one or more times with C₁-C₁₂alkyl orC₁-C₁₂alkoxy, —CO—C₁-C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl and—COO—C₁-C₁₈alkyl.

At present most preferred are compounds A-1 to A-22, B-1 and B-2.Reference is made to claim 9.

In an additional embodiment the present invention is directed tocompounds of formula

whereinA^(1′) and A^(2′) are independently of each other a group of formula

R^(3′) is independently in each occurrence ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹,wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are H orC₁-C₆alkyl, wherein two radicals optionally form a common ring and theseradicals are optionally branched or unbranched and X¹² is a halogenatom, very especially I, or Br; —OS(O)₂CF₃, —OS(O)₂-aryl, especially

—OS(O)₂CH₃, —B(OH)₂, —B(OH)₃—, —BF₃, —B(OY¹)₂,

wherein Y¹ is independently in each occurrence a C₁-C₁₂alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷,Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₂alkyl group, especially —C(CH₃)₂C(CH₃)₂—, —C(CH₃)₂CH₂C(CH₃)₂—, or—CH₂C(CH₃)₂CH₂—, and Y¹³ and Y¹⁴ are independently of each otherhydrogen, or a C₁-C₁₂alkyl group; a, b, c, q, p, R¹, R², R^(1′), R^(2′),R^(1″), R^(2″), R^(1*), R^(2*), Ar¹, Ar², Ar³, A³, A⁴ and A⁵ are asdefined above.

The compound of formula X is preferably a compound of formula

The compounds of the formula X, especially Xa, Xb and Xc areintermediates in the production of polymers and can be used in theproduction of polymers.

Accordingly, the present invention is also directed to polymerscomprising repeating units of formula

wherein A^(1″) and A^(2″) are independently of each other a group offormula

wherein a, b, c, p, q, R¹, R², R^(1′), R^(2′), R^(1″), R^(2″), R^(1*),R^(2*), Ar¹, Ar², Ar³, A³, A⁴ and A⁵ are as defined above. The polymersof the present invention may be used in the production of semiconductordevices. Accordingly, the present invention is also directed tosemiconductor devices comprising a polymer of the present invention.

A process for the preparation of a compound of the formula

(R¹═R²═R^(1*)═R^(2*); A¹=A²) comprises(a) reacting (in the presence of a strong base) 2 mole of a disuccinatewith 1 mole of a nitrile of the formula

and 2 mole of a nitrile of the formula

(b) reacting the compound of formula

obtained in step a) with a halogenide of the formula R¹—X¹⁶ (X¹⁶ ishalogen, especially iodide or bromide) in the presence of a suitablebase, like potassium carbonate, in a suitable solvent, likeN-methylpyrrolidone.

A further synthesis route is, for example, the reaction ofmono-halogenated compounds

under Yamamoto reaction conditions with the aid of a Nickel complex,wherein compounds of formula

are obtained. X¹⁵ is a halogen atom, especially Br, or I. l and z areindependently of each other 1, or 2. k is 0, 1 or 2. r is 0, or 1. R¹,R², R^(1′), R^(2′), A¹ and A² are as defined above. Ar⁴, Ar⁵, Ar⁶, Ar⁷and A³, respectively are as defined above.

Another process for the preparation of compounds of formula

wherein R² is R^(1*), comprises(a) reacting (in the presence of a strong base) 2 moles of a compound offormula

(R²⁰⁰ and R^(200′) are independently of each other a C₁-C₈alkyl group,or a benzyl group) with 1 mole of a di-nitrile compound of the formula

(b) and then alkylation of the compound of formula

obtained in step (a) with a compound R²—X¹⁶ (X¹⁶ is halogen, especiallyiodide or bromide) under basic conditions (preferably K₂CO₃) in a drysolvent such as e.g. dimethylformamide.

The compounds of formula XV and XV′ can be synthesized, for example, inanalogy to the methods described in C. Morton et al., Tetrahedron 58(2002) 5547-5565.

Another process for the preparation of a compound of the formula

(R¹═R²═R^(1*)═R^(2*)) comprises(a) reacting (in the presence of a strong base) 2 mole of a disuccinatewith 1 mole of a nitrile of the formula

and 2 mole of a nitrile of the formula

(b) reacting the compound of formula

obtained in step a) with a halogenide of the formula R¹—X¹⁶ (X¹⁶ ishalogen, especially Br, or I) in the presence of a suitable base, likepotassium carbonate, in a suitable solvent, like N-methyl-pyrrolidone,R¹, R^(1′), R^(2′), A¹, A², A³ and A⁴ are as defined above. Compounds offormula

can be prepared by reacting

wherein X¹⁴ is halogen, such as, for example, Br, or I, withcopper(I)cyanide. The reaction with copper(I)cyanide is carried out in asuitable solvent, like dimethylforamide (DMF) and is carried out at atemperature from about room temperature to about 180° C., preferablyfrom about 100° C. to about 170° C., e.g. at 130° C. Reference is madeto WO2012/041849 and Frank Würthner et al., Chem. Commun., 2011, 47,1767-1769.

Another process for the preparation of compounds of formula

wherein R² is R^(1*), comprises(a) reacting (in the presence of a strong base) 2 moles of a compound offormula

(R²⁰⁰ and R^(200′) are independently of each other a C₁-C₈alkyl group,or a benzyl group) with 1 mole of a di-nitrile compound of the formula

(b) and then alkylation of the compound of formula

obtained in step (a) with a compound R²—X¹⁶ (X¹⁶ is halogen, especiallyiodide or bromide) under basic conditions (preferably K₂CO₃) in a drysolvent such as e.g. dimethylformamide.

Alternatively, compounds of the formula

(R¹═R^(1*); R²═R^(2*),A³ is a group of formula

Ar⁴ is Ar⁷, k is 1, or 2, z is 1,or 2) may be prepared by reacting a compound of formula

with a compound of formula

wherein X^(16′) is —B(OH)₂, —B(OH)₃—, —BF₃, —B(OY¹)₂,

and X¹⁶ is halogen, such as, for example, Br, or I.

The Suzuki reaction is typically conducted at about 0° C. to 180° C. inan aromatic hydrocarbon solvent such as toluene, xylene. Other solventssuch as dimethylformamide, dioxane, dimethoxyethan and tetrahydrofurancan also be used alone, or in mixtures with an aromatic hydrocarbon. Anaqueous base, preferably sodium carbonate or bicarbonate, potassiumphosphate, potassium carbonate or bicarbonate is used as activationagent for the boronic acid, boronate and as the HBr scavenger. Acondensation reaction may take 0.2 to 100 hours. Organic bases, such as,for example, tetraalkylammonium hydroxide, and phase transfer catalysts,such as, for example TBAB, can promote the activity of the boron (see,for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003)1407 and references cited therein). Other variations of reactionconditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59(1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol.Rapid Commun. 17 (1996) 239-252.

The compounds of the present invention can also be sythesized by theStille coupling (see, for example, Babudri et al, J. Mater. Chem., 2004,14, 11-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508). Inorder to carry out the process, tin compounds

wherein X^(16′) is —SnR²⁰⁷R²⁰⁸R²⁰⁹, and the halogen compound

are preferably introduced into one or more inert organic solvents andstirred at a temperature of from 0 to 200° C., preferably from 30 to170° C. for a period of from 1 hour to 200 hours, preferably from 5hours to 150 hours.

Reference is made to WO2009/047104 and WO2012/041849 with respect to thepreparation of the strating materials and the compounds of formula I.

In the above Stille and Suzuki coupling reactions the halogen X¹⁶ on thehalogenated reaction partner can be replaced with the X^(16′) moiety andat the same time the X^(16′) moiety of the other reaction partner isreplaced by X¹⁶.

Compounds of formula Ib can be prepared in analogy to the synthesis ofcompounds of formula Ia via Suzuki, or Stille reaction starting from thecorresponding building blocks, e.g.: Two equivalents of a compound offormula

are reacted with one equivalent of a compound of formula

to give a compound of formula

The compounds, wherein R¹, R², R^(1′), R², R^(1″), R^(2″), R^(1*) and/orR^(2*) are hydrogen can be obtained by using a protecting group whichcan be removed after synthesis of the precursor compound (see, forexample, EP-A-0648770, EP-A-0648817, EP-A-0742255, EP-A-0761772,WO98/32802, WO98/45757, WO98/58027, WO99/01511, WO00/17275, WO00/39221,WO00/63297 and EP-A-1086984). Conversion of the precursor compound intothe desired final compound is carried out by means of fragmentationunder known conditions, for example thermally, optionally in thepresence of an additional catalyst, for example the catalysts describedin WO00/36210.

An example of such a protecting group is group of formula

wherein L is any desired group suitable for imparting solubility.

L is preferably a group of formula

wherein Z¹, Z² and Z³ are independently of each other C₁-C₆alkyl,Z⁴ and Z⁸ are independently of each other C₁-C₆alkyl, C₁-C₆alkylinterrupted by oxygen, sulfur or N(Z¹²)₂, or unsubstituted orC₁-C₆alkyl-, C₁-C₆alkoxy-, halo-, cyano- or nitro-substituted phenyl orbiphenyl,Z⁵, Z⁶ and Z⁷ are independently of each other hydrogen or C₁-C₆alkyl,Z⁹ is hydrogen, C₁-C₆alkyl or a group of formula

Z¹⁰ and Z¹¹ are each independently of the other hydrogen, C₁-C₆alkyl,C₁-C₆alkoxy, halogen, cyano, nitro, N(Z¹²)₂, or unsubstituted or halo-,cyano-, nitro-, C₁-C₆alkyl- or C₁-C₆alkoxy-substituted phenyl,Z¹² and Z¹³ are C₁-C₆alkyl, Z¹⁴ is hydrogen or C₁-C₆alkyl, and Z¹⁵ ishydrogen, C₁-C₆alkyl, or unsubstituted or C₁-C₆alkyl-substituted phenyl,Q is p,q-C₂-C₆alkylene unsubstituted or mono- or poly-substituted byC₁-C₆alkoxy, C₁-C₆alkylthio or C₂-C₁₂dialkylamino, wherein p and q aredifferent position numbers,X is a hetero atom selected from the group consisting of nitrogen,oxygen and sulfur, m′ being the number 0 when X is oxygen or sulfur andm being the number 1 when X is nitrogen, andL¹ and L² are independently of each other unsubstituted or mono- orpoly-C₁-C₁₂ alkoxy-, —C₁-C₁₂alkylthio-, —C₂-C₂₄dialkylamino-,—C₆-C₁₂aryloxy-, —C₆-C₁₂arylthio-, —C₇-C₂₄alkylarylamino- or—C₁₂-C₂₄diarylamino-substituted C₁-C₆alkyl or[-(p′,q′—C₂-C₆alkylene)-Z-]_(n′)-C₁-C₆alkyl, n′ being a number from 1 to1000, p′ and q′ being different position numbers, each Z independentlyof any others being a hetero atom oxygen, sulfur orC₁-C₁₂alkyl-substituted nitrogen, and it being possible forC₂-C₆alkylene in the repeating [—C₂-C₆alkylene-Z—] units to be the sameor different,and L₁ and L₂ may be saturated or unsaturated from one to ten times, maybe uninterrupted or interrupted at any location by from 1 to 10 groupsselected from the group consisting of —(C═O)— and —C₆H₄—, and may carryno further substituents or from 1 to 10 further substituents selectedfrom the group consisting of halogen, cyano and nitro. Most preferred Lis a group of formula

The disuccinates to be used in the process according to the inventioninclude dialkyl, diaryl or monoalkyl-monoaryl succinates. The dialkyland diaryl succinates may also be asymmetrical. However, it is preferredto use symmetrical disuccinates, most preferably symmetrical dialkylsuccinates, most preferably symmetrical dialkyl succinates. If a diarylor monoaryl-monoalkyl succinate is employed, aryl denotes preferablyphenyl which is unsubstituted or substituted by halogen such aschlorine, C₁₋₆-alkyl such as ethyl, methyl, isopropyl or tert-butyl, orC₁₋₆-alkoxy such as methoxy or ethoxy. The preferred meaning of aryl isunsubstituted phenyl. If a dialkyl or monoalkyl-monoaryl succinate isemployed, then alkyl may be unbranched or branched, preferably branched,and may contain preferably 1 to 18, in particular 1 to 12, moreparticularly 1 to 8 and more preferably 1 to 5, carbon atoms. Branchedalkyl is preferably sec- or tert-alkyl, for example, isopropyl,sec-butyl, tert-butyl, tert-amyl and cyclohexyl.

Examples of disuccinates are dimethyl succinate, diethyl succinate,dipropyl succinate, dibutyl succinate, dipentyl succinate, dihexylsuccinate, diheptyl succinate, dioctyl succinate, diisopropyl succinate,di-sec-butyl succinate, di-tert-butyl succinate, di-tert-amyl succinate,di-[1,1-dimethylbutyl]succinate, di-[1,1,3,3-tetramethylbutyl]succinate,di-[1,1dimethylpentyl]succinate, di-[1-methyl-ethylbutyl]succinate,di-[1,1-diethylpropyl]succinate, diphenyl succinate,di-[4-methylphenyl]succinate, di-[4-chlorophenyl]succinate,monoethyl-monophenyl succinate, and dicyclohexyl succinate. Mostpreferably, the starting disuccinate is diisopropyl succinate.

The disuccinates are known compounds and may be prepared by knownmethods.

Typically, the nitriles and the disuccinate are used in stoichiometricproportions. It can be advantageous to use the nitriles to be reactedwith the disuccinate in more than only stoichiometric proportions. Anexcess of disuccinate over the nitrile can often have a positiveinfluence on the yield, in which case the excess may be up to twice thestoichiometrically required amount of disuccinate.

The reaction of the disuccinate with the nitriles is carried out in anorganic solvent. Examples of suitable solvents are primary, secondary ortertiary alcohols containing 1 to 10 carbon atoms, for example,methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,tert-butanol, n-pentanol, 2-methyl-2-butanol, 2-methyl-2-pentanol,3-methyl-3pentanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol,2,4,4-trimethyl-2-pentanol, or glycols such as ethylene glycol ordiethylene glycol; and also ethers such as tetrahydrofuran or dioxan, orglycol ethers such as ethylene glycol methyl ether, ethylene glycolethyl ether, diethylene glycol monomethyl ether or diethylene glycolmonoethyl ether; as well as dipolar aprotic solvents such asacetonitrile, benzonitrile, dimethylformamide, N,N-dimethylacetamide,nitrobenzene, N-methylpyrrolidone; aliphatic or aromatic hydrocarbonssuch as benzene or benzene substituted by alkyl, alkoxy or halogen, forexample, toluene, xylene, anisole or chlorobenzene; or aromaticheterocyclic compounds such as pyridine, picoline or quinoline. Mixturesof the above solvents may also be used. It is convenient to use 5 to 20parts be weight of solvent per 1 part by weight of reactants.

In the process according to the invention, it is preferred to use analcohol as solvent, in particular a secondary or tertiary alcohol.Preferred tertiary alcohols are tert-butanol and tert-amyl alcohol.Mixtures of these preferred solvents with aromatic hydrocarbons such astoluene or xylene, or halogen-substituted benzene such as chlorobenzene,are also useful.

The process according to the invention is carried out in the presence ofa strong base. Suitable strong bases are in particular the alkali metalsthemselves such as lithium, sodium or potassium, or alkali metal amidessuch as lithium amide, sodium amide or potassium amide, or alkali metalhydrides such as lithium, sodium or potassium hydride, or alkaline earthmetal alcoholates or alkali metal alcoholates which are derivedpreferably from primary, secondary or tertiary aliphatic alcoholscontaining from 1 to 10 carbon atoms, for example, lithium methylate,sodium methylate or potassium methylate, or lithium, sodium or potassiumethylate, lithium, sodium or potassium n-propylate, lithium, sodium orpotassium iso-propylate, lithium, sodium or potassium n-butylate,lithium, sodium or potassium sec-butylate, lithium, sodium or potassiumtert-butylate, lithium, sodium or potassium 2-methyl-2-butylate,lithium, sodium or potassium 2-methyl-2-pentylate, lithium, sodium orpotassium 3-methyl-3-pentylate, lithium, sodium or potassium3-ethyl-3-pentylate or lithium, sodium or potassium 3-ethyl-3-pentylate.Additionally, a mixture of these bases may also be employed.

The preferred strong base is an alkali metal alcoholate, the alkalimetals being preferably sodium or potassium and the alcoholate beingpreferably derived from a secondary or tertiary alcohol. Particularlypreferred strong bases are therefore, for example, sodium or potassiumisopropylate, sodium or potassium sec-butylate, sodium or potassiumtert-butylate and sodium or potassium tert-amylate. Moreover, the alkalimetal alcoholates may be prepared in situ by reacting the appropriatealcohol with the alkali metal, alkali metal hydride or alkali metalamide.

The strong base is employed in an amount of preferably from about 0.1 toabout 10 moles, most preferably from about 1.9 to about 4.0 moles, basedon one mole of the disuccinate. Although a stoichiometric amount of basemay suffice, an excess of base has been found to have an advantageouseffect on the yield.

Halogen is fluorine, chlorine, bromine and iodine.

C₁-C₂₅alkyl (C₁-C₁₈alkyl) is typically linear or branched, wherepossible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3pentyl,2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl,1,1,3,3,5,5hexamethylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl.C₁-C₈alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C₁-C₄alkyl is typicallymethyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,tert.-butyl. A haloalkyl group is an alkyl group, wherein one, or morethan one hydrogen atoms are repled by halogen atoms.

C₂-C₂₅alkenyl (C₂-C₁₈alkenyl) groups are straight-chain or branchedalkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl,2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl,3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl,n-dodec-2-enyl or n-octadec-4-enyl.

C₂₋₂₅alkynyl (C₂₋₁₈alkynyl) is straight-chain or branched and preferablyC₂₋₈alkynyl, which may be unsubstituted or substituted, such as, forexample, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl,2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl,1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl,trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl,1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, besubstituted by any acyclic substituents, but are preferablyunsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkylthiogroups as exemplified further below. The term “aliphatic group”comprises also alkyl groups wherein certain non-adjacent carbon atomsare replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CH₃. The latter group canbe regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

An aliphatic hydrocarbon group having up to 25 carbon atoms is a linearor branched alkyl, alkenyl or alkynyl (also spelled alkinyl) grouphaving up to 25 carbon atoms as exemplified above.

Alkylene is bivalent alkyl, i.e. alkyl having two (instead of one) freevalencies, e.g. trimethylene or tetramethylene.

Alkenylene is bivalent alkenyl, i.e. alkenyl having two (instead of one)free valencies, e.g. —CH₂—CH═CH—CH₂—.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, besubstituted by any acyclic substituents, but are preferablyunsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkylthiogroups as exemplified further below. The term “aliphatic group”comprises also alkyl groups wherein certain non-adjacent carbon atomsare replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CH₃. The latter group canbe regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

A cycloaliphatic hydrocarbon group is a cycloalkyl or cycloalkenyl groupwhich may be substituted by one or more aliphatic and/or cycloaliphatichydrocarbon groups.

A cycloaliphatic-aliphatic group is an aliphatic group substituted by acycloaliphatic group, wherein the terms “cycloaliphatic” and “aliphatic”have the meanings given herein and wherein the free valency extends fromthe aliphatic moiety. Hence, a cycloaliphatic-aliphatic group is forexample a cycloalkyl-alkyl group.

A cycloalkyl-alkyl group is an alkyl group substituted by a cycloalkylgroup, e.g. cyclohexyl-methyl.

A “cycloalkenyl group” means an unsaturated alicyclic hydrocarbon groupcontaining one or more double bonds, such as cyclopentenyl,cyclopentadienyl, cyclohexenyl and the like, which may be unsubstitutedor substituted by one or more aliphatic and/or cycloaliphatichydrocarbon groups and/or condensed with phenyl groups.

A bivalent group of the formula

wherein R⁷⁰ and R⁷¹ together represent alkylene or alkenylene which maybe both bonded via oxygen and/or sulfur to the thienyl residue and whichmay both have up to 25 carbon atoms, is e.g. a group of the formula

wherein A represents linear or branched alkylene having up to 25 carbonatoms, preferably ethylene or propylene which may be substituted by oneor more alkyl groups, and Y represents oxygen or sulphur. For example,the bivalent group of the formula —Y-A-O— represents —O—CH₂—CH₂—O— or—O—CH₂—CH₂—CH₂—O—.

C₁-C₂₅alkoxy groups (C₁-C₁₈alkoxy groups) are straight-chain or branchedalkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy,octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy,tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy andoctadecyloxy. Examples of C₁-C₈alkoxy are methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy,2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy,n-octoxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferablyC₁-C₄alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy. The term “alkylthiogroup” means the same groups as the alkoxy groups, except that theoxygen atom of the ether linkage is replaced by a sulfur atom.

C₁-C₁₈perfluoroalkyl, especially C₁-C₄perfluoroalkyl, is a branched orunbranched radical such as for example —CF₃, —CF₂CF₃, —CF₂CF₂CF₃,—CF(CF₃)₂, —(CF₂)₃CF₃, and —C(CF₃)₃.

The term “carbamoyl group” is typically a C₁₋₁₈carbamoyl radical,preferably C₁₈ carbamoyl radical, which may be unsubstituted orsubstituted, such as, for example, carbamoyl, methylcarbamoyl,ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl,dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

The term “alkanoyl” represents an alkyl group attached to the parentmolecular group through a carbonyl group and is exemplified by formyl,acetyl, propionyl, and butanoyl.

The term “silyl group” means a group of formula —SiR⁶²R⁶³R⁶⁴, whereinR⁶², R⁶³ and R⁶⁴ are independently of each other a C₁-C₈alkyl group, inparticular a C₁-C₄ alkyl group, a C₆-C₂₄aryl group, or aC₇-C₁₂aralkylgroup, such as a trimethylsilyl group. The term “siloxanylgroup” means a group of formula —O—SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³ and R⁶⁴are as defined above, such as a trimethylsiloxanyl group.

A cycloalkyl group is typically C₃-C₁₂cycloalkyl, such as, for example,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl,cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted orsubstituted. The cycloalkyl group, or cycloalkenyl group, in particulara cyclohexyl group, can be condensed one or two times by phenyl whichcan be substituted one to three times with C₁-C₄-alkyl, halogen andcyano. Examples of such condensed cyclohexyl groups are:

in particular

wherein R¹⁵¹, R¹⁵², R¹⁵³, R¹⁵⁴, R¹⁵⁵ and R¹⁵⁶ are independently of eachother C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano, in particularhydrogen.

C₆-C₂₄aryl (C₆-C₁₈aryl) is typically phenyl, indenyl, azulenyl,naphthyl, biphenyl, as-indacenyl, s-indacenyl, acenaphthylenyl,fluorenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl,naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, oranthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl,9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may beunsubstituted or substituted. Examples of C₆-C₁₂aryl are phenyl,1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or9-phenanthryl, which may be unsubstituted or substituted.

C₇-C₂₅aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl,α,α-dimethylbenzyl, ω-phenyl-butyl, ω, ω-dimethyl-ω-phenyl-butyl,ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl orω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such as benzyl,2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl,ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, andparticularly preferred C₇-C₁₂aralkyl such as benzyl, 2-benzyl-2-propyl,β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, orω,ω-dimethyl-ω-phenyl-butyl, in which both the aliphatic hydrocarbongroup and aromatic hydrocarbon group may be unsubstituted orsubstituted. Preferred examples are benzyl, 2-phenylethyl,β-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl.

Heteroaryl is typically C₂-C₂₀heteroaryl, i.e. a ring with five to sevenring atoms or a condensed ring system, wherein nitrogen, oxygen orsulfur are the possible hetero atoms, and is typically an unsaturatedheterocyclic group with five to 30 atoms having at least six conjugatedπ-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl,thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl,isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl,pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl,pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl,quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl,chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl,carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl,pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl,isoxazolyl, furazanyl or phenoxazinyl, which can be unsubstituted orsubstituted.

Possible substituents of the above-mentioned groups are C₁-C₈alkyl, ahydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen,halo-C₁-C₈alkyl, a cyano group, a carbamoyl group, a nitro group or asilyl group, especially C₁-C₈alkyl, C₁-C₈alkoxy, C₁-C₈alkylthio,halogen, halo-C₁-C₈alkyl, or a cyano group.

C₁-C₂₅alkyl (C₁-C₁₈alkyl) interrupted by one or more O is, for example,(CH₂CH₂O)₁₋₉R⁴⁴, where R⁴⁴ is H or C₁-C₁₀alkyl,CH₂—CH(OR^(y′))—CH₂—O—R^(y), where R^(y) is C₁-C₂₅alkyl (C₁-C₁₈alkyl),and R^(y′) embraces the same definitions as R^(y) or is H.

If a substituent, such as, for example R³, occurs more than one time ina group, it can be different in each occurrence.

Advantageously, the compounds of the present invention, or an organicsemiconductor material, layer or component, comprising the compounds ofthe present invention can be used in organic photovoltaics (solar cells)and photodiodes, or in an organic field effect transistor (OFET).

The compounds of the formula I can show p-type transistor behavior andcan be used as the semiconductor layer in semiconductor devices.Accordingly, the present invention also relates to a semiconductordevice comprising as a semiconducting effective means a compound of theformula I.

The invention relates especially to a semiconductor device comprising asa semiconducting effective means a compound of the formula I describedin the Examples selected from the compounds having the formulae A-1 toA-22, B-1 and B-2, respectively, which are depicted in claim 10.

Preferably said semiconductor device is a diode, a photodiode, a sensor,an organic field effect transistor (OFET), a transistor for flexibledisplays, or a solar cell, or a device containing a diode and/or anorganic field effect transistor, and/or a solar cell. There are numeroustypes of semiconductor devices. Common to all is the presence of one ormore semiconductor materials. Semiconductor devices have been described,for example, by S. M. Sze in Physics of Semiconductor Devices, 2^(nd)edition, John Wiley and Sons, New York (1981). Such devices includerectifiers, transistors (of which there are many types, including p-n-p,n-p-n, and thin-film transistors), light emitting semiconductor devices(for example, organic light emitting diodes in display applications orbacklight in e.g. liquid crystal displays), photoconductors, currentlimiters, solar cells, thermistors, p-n junctions, field-effect diodes,Schottky diodes, and so forth. In each semiconductor device, thesemiconductor material is combined with one or more metals and/orinsulators to form the device. Semiconductor devices can be prepared ormanufactured by known methods such as, for example, those described byPeter Van Zant in Microchip Fabrication, Fourth Edition, McGraw-Hill,New York (2000). In particular, organic electronic components can bemanufactured as described by D. R. Gamota et al. in Printed Organic andMolecular Electronics, Kluver Academic Publ., Boston, 2004.

A particularly useful type of transistor device, the thin-filmtransistor (TFT), generally includes a gate electrode, a gate dielectricon the gate electrode, a source electrode and a drain electrode adjacentto the gate dielectric, and a semiconductor layer adjacent to the gatedielectric and adjacent to the source and drain electrodes (see, forexample, S. M. Sze, Physics of Semiconductor Devices, 2^(nd) edition,John Wiley and Sons, page 492, New York (1981)). These components can beassembled in a variety of configurations. More specifically, an organicthin-film transistor (OTFT) has an organic semiconductor layer.

Typically, a substrate supports the OTFT during manufacturing, testing,and/or use. Optionally, the substrate can provide an electrical functionfor the OTFT. Useful substrate materials include organic and inorganicmaterials. For example, the substrate can comprise silicon materialsinclusive of various appropriate forms of silicon, inorganic glasses,ceramic foils, polymeric materials (for example, acrylics, polyester,epoxies, polyamides, polycarbonates, polyimides, polyketones,poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene)(sometimes referred to as poly(ether ether ketone) or PEEK),polynorbornenes, polyphenyleneoxides, poly(ethylenenaphthalenedicarboxylate) (PEN), poly(ethylene terephthalate) (PET),poly(phenylene sulfide) (PPS)), filled polymeric materials (for example,fiber-reinforced plastics (FRP)), and coated metallic foils. Thesubstrate can have any suitable thickness, preferably in the range of100 m to 10 mm, even more preferably from 10 □m to 1 mm.

The gate electrode can be any useful conductive material. For example,the gate electrode can comprise doped silicon, or a metal, such asaluminum, chromium, gold, silver, nickel, palladium, platinum, tantalum,and titanium. Conductive oxides, such as indium tin oxide (ITO), orconducting inks/pastes comprised of carbon black/graphite or colloidalsilver dispersions, optionally containing polymer binders can also beused. Conductive polymers also can be used, for example polyaniline orpoly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS). Inaddition, alloys, combinations, and multilayers of these materials canbe useful. In some OTFTs, the same material can provide the gateelectrode function and also provide the support function of thesubstrate. For example, doped silicon can function as the gate electrodeand support the OTFT.

The gate dielectric is generally provided on the gate electrode. Thisgate dielectric electrically insulates the gate electrode from thebalance of the OTFT device. Useful materials for the gate dielectric cancomprise, for example, an inorganic electrically insulating material.

The gate dielectric (insulator) can be a material, such as, an oxide,nitride, or it can be a material selected from the family offerroelectric insulators (e.g. organic materials such as poly(vinylidenefluoride/trifluoroethylene or poly(m-xylylene adipamide)), or it can bean organic polymeric insulator (e.g. poly(methacrylate)s,poly(acrylate)s, polyimides, benzocyclobutenes (BCBs), parylenes,polyvinylalcohol, polyvinylphenol (PVP), polystyrenes, polyester,polycarbonates) as for example described in J. Veres et al. Chem. Mat.2004, 16, 4543 or A. Facchetti et al. Adv. Mat. 2005, 17, 1705. Specificexamples of materials useful for the gate dielectric includestrontiates, tantalates, titanates, zirconates, aluminum oxides, siliconoxides, tantalum oxides, titanium oxides, silicon nitrides, bariumtitanate, barium strontium titanate, barium zirconate titanate, zincselenide, and zinc sulphide, including but not limited toPbZr_(x)Ti_(1-x)O₃ (PZT), Bi₄Ti₃O₁₂, BaMgF₄, Ba(Zr_(1-x)Ti_(x))O₃ (BZT).In addition, alloys, hybride materials (e.g. polysiloxanes ornanoparticle-filled polymers) combinations, and multilayers of thesematerials can be used for the gate dielectric. The thickness of thedielectric layer is, for example, from about 10 to 1000 nm, with a morespecific thickness being about 100 to 500 nm, providing a capacitance inthe range of 0.1-100 nanofarads (nF).

The source electrode and drain electrode are separated from the gateelectrode by the gate dielectric, while the organic semiconductor layercan be over or under the source electrode and drain electrode. Thesource and drain electrodes can be any useful conductive materialfavourably providing a low resistance ohmic contact to the semiconductorlayer. Useful materials include most of those materials described abovefor the gate electrode, for example, aluminum, barium, calcium,chromium, gold, silver, nickel, palladium, platinum, titanium,polyaniline, PEDOT:PSS, other conducting polymers, alloys thereof,combinations thereof, and multilayers thereof. Some of these materialsare appropriate for use with n-type semiconductor materials and othersare appropriate for use with p-type semiconductor materials, as is knownin the art.

The thin film electrodes (that is, the gate electrode, the sourceelectrode, and the drain electrode) can be provided by any useful meanssuch as physical vapor deposition (for example, thermal evaporation orsputtering) or (ink jet) printing methods. The patterning of theseelectrodes can be accomplished by known methods such as shadow masking,additive photolithography, subtractive photolithography, printing,microcontact printing, and pattern coating.

The present invention further provides a thin film transistor devicecomprising a plurality of electrically conducting gate electrodesdisposed on a substrate; a gate insulator layer disposed on saidelectrically conducting gate electrodes; a plurality of sets ofelectrically conductive source and drain electrodes disposed on saidinsulator layer such that each of said sets is in alignment with each ofsaid gate electrodes; an organic semiconductor layer disposed in thechannel between source and drain electrodes on said insulator layersubstantially overlapping said gate electrodes; wherein said organicsemiconductor layer comprise a compound of the formula I.

The present invention further provides a process for preparing a thinfilm transistor device comprising the steps of:

depositing a plurality of electrically conducting gate electrodes on asubstrate;

depositing a gate insulator layer on said electrically conducting gateelectrodes;

depositing a plurality of sets of electrically conductive source anddrain electrodes on said layer such that each of said sets is inalignment with each of said gate electrodes;

depositing a layer comprising a compound of the formula I on saidinsulator layer such that said layer comprising the compound of formulaI substantially overlaps said gate electrodes, thereby producing thethin film transistor device.

The above-mentioned layer comprising a compound of formula I mayadditionally comprise at least another material. The other material canbe, but is not restricted to another compound of the formula I, asemi-conducting polymer, a polymeric binder, organic small moleculesdifferent from a compound of the formula I, carbon nanotubes, afullerene derivative, inorganic particles (quantum dots, quantum rods,quantum tripods, TiO₂, ZnO etc.), conductive particles (Au, Ag etc.),and insulator materials like the ones described for the gate dielectric(PET, PS etc.). As stated above, the semiconductive layer can also becomposed of a mixture of one or more small molecules of the formula Iand a polymeric binder. The ratio of the small molecules of formula I tothe polymeric binder can vary from 5 to 95 percent. Preferably, thepolymeric binder is a semicristalline polymer such as polystyrene (PS),high-density polyethylene (HDPE), polypropylene (PP) andpolymethylmethacrylate (PMMA). With this technique, a degradation of theelectrical performance can be avoided (cf. WO 2008/001123 A1).

Any suitable substrate can be used to prepare the thin films of thecompounds of the formula I. Preferably, the substrate used to preparethe above thin films is a metal, silicon, plastic, paper, coated paper,fabric, glass or coated glass.

Alternatively, a TFT is fabricated, for example, by solution deposition,or vacuum deposition of a compound of the formula I on a highly dopedsilicon substrate covered with a thermally grown oxide layer followed byvacuum deposition and patterning of source and drain electrodes.

In yet another approach, a TFT is fabricated by deposition of source anddrain electrodes on a highly doped silicon substrate covered with athermally grown oxide and then solution deposition of the compound ofthe formula I to form a thin film.

The gate electrode could also be a patterned metal gate electrode on asubstrate or a conducting material such as a conducting polymer, whichis then coated with an insulator applied either by solution coating orby vacuum deposition on the patterned gate electrodes.

Any suitable solvent can be used to dissolve, and/or disperse a compoundof the formula I, provided it is inert and can be removed partly, orcompletely from the substrate by conventional drying means (e.g.application of heat, reduced pressure, airflow etc.). Suitable organicsolvents for processing the semiconductors of the invention include, butare not limited to, aromatic or aliphatic hydrocarbons, halogenated suchas chlorinated or fluorinated hydrocarbons, esters, ethers amides, suchas chloroform, tetrachloroethane, tetrahydrofuran, toluene, tetraline,anisole, xylene, ethyl acetate, methyl ethyl ketone, dimethyl formamide,dichlorobenzene, trichlorobenzene, propylene glycol monomethyl etheracetate (PGMEA) and mixtures thereof. The solution, and/or dispersion isthen applied by a method, such as, spin-coating, dip-coating, screenprinting, microcontact printing, doctor blading or other solutionapplication techniques known in the art on the substrate to obtain thinfilms of the semiconducting material.

The term “dispersion” covers any composition comprising a compound ofthe formula I, which is not fully dissolved in a solvent. The dispersioncan be done selecting a composition including at least a compound offormula I, or a mixture containing a compound of formula I, and asolvent, wherein the polymer exhibits lower solubility in the solvent atroom temperature but exhibits greater solubility in the solvent at anelevated temperature, wherein the composition gels when the elevatedtemperature is lowered to a first lower temperature without agitation;

-   -   dissolving at the elevated temperature at least a portion of the        compound of the formula I in the solvent; lowering the        temperature of the composition from the elevated temperature to        the first lower temperature; agitating the composition to        disrupt any gelling, wherein the agitating commences at any time        prior to, simultaneous with, or subsequent to the lowering the        elevated temperature of the composition to the first lower        temperature; depositing a layer of the composition wherein the        composition is at a second lower temperature lower than the        elevated temperature; and drying at least partially the layer.

The dispersion can also be constituted of (a) a continuous phasecomprising a solvent, a binder resin, and optionally a dispersing agent,and (b) a disperse phase comprising a compound of formula I, or amixture containing a compound of formula I of the present invention. Thedegree of solubility of the compound of formula I in the solvent mayvary for example from 0.5% to about 20% solubility, particularly from 1%to about 5% solubility.

Preferably, the thickness of the organic semiconductor layer is in therange of from about 5 to about 1000 nm, especially the thickness is inthe range of from about 10 to about 100 nm.

The compounds of the formula I can be used alone or in combination asthe organic semiconductor layer of the semiconductor device. The layercan be provided by any useful means, such as, for example, vapordeposition and printing techniques. The compounds of the formula I whichare sufficiently soluble in organic solvents can be solution depositedand patterned (for example, by spin coating, dip coating, ink jetprinting, gravure printing, flexo printing, offset printing, screenprinting, microcontact (wave)-printing, drop or zone casting, or otherknown techniques).

The compounds of the formula I can be used in integrated circuitscomprising a plurality of OTFTs, as well as in various electronicarticles. Such articles include, for example, radiofrequencyidentification (RFID) tags, backplanes for flexible displays (for usein, for example, personal computers, cell phones, or handheld devices),smart cards, memory devices, sensors (e.g. light-, image-, bio-, chemo-,mechanical- or temperature sensors), especially photodiodes, or securitydevices and the like. Due to its ambi-polarity the material can also beused in Organic Light Emitting Transistors (OLET).

In addition, the invention provides organic photovoltaic (PV) devices(solar cells) comprising a compound of the formula I. The structure oforganic photovoltaic devices (solar cells) is, for example, described inC. Deibel et al. Rep. Prog. Phys. 73 (2010) 096401 and Christoph Brabec,Energy Environ. Sci 2. (2009) 347-303.

The PV device comprise in this order:

(a) a cathode (electrode),

(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) an anode (electrode),

(f) a substrate.

The photoactive layer comprises the compounds of the formula I.Preferably, the photoactive layer is made of a compound of the formulaI, as an electron donor and an acceptor material, like a fullerene,particularly a functionalized fullerene PCBM, as an electron acceptor.As stated above, the photoactive layer may also contain a polymericbinder. The ratio of the small molecules of formula I to the polymericbinder can vary from 5 to 95 percent. Preferably, the polymeric binderis a semicristalline polymer such as polystyrene (PS), high-densitypolyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate(PMMA).

The fullerenes useful in this invention may have a broad range of sizes(number of carbon atoms per molecule). The term fullerene as used hereinincludes various cage-like molecules of pure carbon, includingBuckminsterfullerene (C₆₀) and the related “spherical” fullerenes aswell as carbon nanotubes. Fullerenes may be selected from those known inthe art ranging from, for example, C₂₀-C₁₀₀₀. Preferably, the fullereneis selected from the range of C₆₀ to C₉₆. Most preferably the fullereneis C₆₀ or C₇₀, such as [60]PCBM, or [70]PCBM. It is also permissible toutilize chemically modified fullerenes, provided that the modifiedfullerene retains acceptor-type and electron mobility characteristics.The acceptor material can also be a material selected from the groupconsisting of another compound of formula I or any semi-conductingpolymer provided that the polymers retain acceptor-type and electronmobility characteristics, organic small molecules, carbon nanotubes,inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂,ZnO etc.).

For heterojunction solar cells (bulk heterojunction solar cells) theactive layer comprises preferably a mixture of a compound of the formulaI and a fullerene, such as [60]PCBM (=6,6-phenyl-C₆₁-butyric acid methylester), or [70]PCBM, in a weight ratio of 1:1 to 1:3. MethanofullerenePhenyl-C₆₁-Butyric-Acid-Methyl-Ester ([60]PCBM), i.e.1-[3-(methoxycarbonyl)propyl]-1-phenyl-[6.6]C₆₁-3′H-cyclopropa[1,9][5,6]fullerene-C₆₀-lh-3′-butanoicacid 3′-phenyl methyl ester, is an effective solution processable n-typeorganic semiconductor. It is blended with conjugated polymers withnano-particles such as C₆₀.

The electrodes are preferably composed of metals or “metal substitutes”.Herein the term “metal” is used to embrace both materials composed of anelementally pure metal, e.g., Mg, and also metal alloys which arematerials composed of two or more elementally pure metals, e.g., Mg andAg together, denoted Mg:Ag. Here, the term “metal substitute” refers toa material that is not a metal within the normal definition, but whichhas the metal-like properties that are desired in certain appropriateapplications. Commonly used metal substitutes for electrodes and chargetransfer layers would include doped wide-bandgap semiconductors, forexample, transparent conducting oxides such as indium tin oxide (ITO),gallium indium tin oxide (GITO), and zinc indium tin oxide (ZITO).Another suitable metal substitute is the transparent conductive polymerpolyanaline (PANI) and its chemical relatives, or PEDOT:PSS. Metalsubstitutes may be further selected from a wide range of non-metallicmaterials, wherein the term “non-metallic” is meant to embrace a widerange of materials provided that the material is free of metal in itschemically uncombined form.

Highly transparent, non-metallic, low resistance cathodes or highlyefficient, low resistance metallic/non-metallic compound cathodes are,for example, disclosed in U.S. Pat. No. 6,420,031 and U.S. Pat. No.5,703,436.

The substrate can be, for example, a plastic (flexible substrate), orglass substrate.

In another preferred embodiment of the invention, a smoothing layer issituated between the anode and the photoactive layer. A preferredmaterial for this smoothing layer comprises a film of3,4-polyethylenedioxythiophene (PEDOT), or3,4-polyethylenedioxy-thiophene:polystyrene-sulfonate (PEDOT:PSS).

In a preferred embodiment of the present invention, the photovoltaiccell comprises, as described for example, in U.S. Pat. No. 6,933,436 atransparent glass carrier, onto which an electrode layer made ofindium/tin oxide (ITO) is applied. This electrode layer generally has acomparatively rough surface structure, so that it is covered with asmoothing layer made of a polymer, typically PEDOT, which is madeelectrically conductive through doping. The photoactive layer is made oftwo components, has a layer thickness of, for example, 100 nm to a fewμm depending on the application method, and is applied onto thissmoothing layer. The photoactive layer is made of a compound of theformula I, as an electron donor and a fullerene, particularlyfunctionalized fullerene PCBM, as an electron acceptor. These twocomponents are mixed with a solvent and applied as a solution onto thesmoothing layer by, for example, the spin-coating method, the dropcasting method, the Langmuir-Blodgett (“LB”) method, the ink jetprinting method and the dripping method. A squeegee or printing methodcould also be used to coat larger surfaces with such a photoactivelayer. Instead of toluene, which is typical, a dispersion agent such aschlorobenzene is preferably used as a solvent. Among these methods, thevacuum deposition method, the spin-coating method, the ink jet printingmethod and the casting method are particularly preferred in view of easeof operation and cost.

In the case of forming the layer by using the spin-coating method, thecasting method and ink jet printing method, the coating can be carriedout using a solution and/or dispersion prepared by dissolving, ordispersing the composition in a concentration of from 0.01 to 90% byweight in an appropriate organic solvent such as benzene, toluene,xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide,acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide,chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

Before a counter electrode is applied, a thin transition layer, whichmust be electrically insulating, having a layer thickness of, forexample, 0.6 nm, is applied to the photoactive layer. In this exemplaryembodiment, this transition layer is made of an alkali halogenide,namely a lithium fluoride, which is vapor deposited in a vacuum of2·10⁻⁶ torr at a rate of 0.2 nm/minute.

If ITO is used as a hole-collecting electrode, aluminum, which is vapordeposited onto the electrically insulating transition layer, is used asan electron-collecting electrode. The electric insulation properties ofthe transition layer obviously prevent influences which hinder thecrossing of the charge carrier from being effective, particularly in thetransition region from the photoactive layer to the transition layer.

In a further embodiment of the invention, one or more of the layers maybe treated with plasma prior to depositing the next layer. It isparticularly advantageous that prior to the deposition of the PEDOT:PSSlayer the anode material is subjected to a mild plasma treatment.

As an alternative to PEDOT:PSS a crosslinkable hole-transport materialbased on triarylamines as referenced in Macromol. Rapid Commun. 20,224-228 (1999) can be used. In addition to the triarylamine material thelayer can also include an electron acceptor to improve electrontransport. Such compounds are disclosed in US 2004/0004433. Preferably,the electron acceptor material is soluble in one or more organicsolvents. Typically, the electron acceptor material is present in therange of 0.5 to 20% by weight of the triarylamine material.

The photovoltaic (PV) device can also consist of multiple junction solarcells that are processed on top of each other in order to absorb more ofthe solar spectrum. Such structures are, for example, described in App.Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006)and WO2004/112161 and Christoph Brabec, Energy Environ. Sci 2. (2009)347-303.

A so called ‘tandem solar cell’ comprise in this order:

(a) a cathode (electrode),

(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) a middle electrode (such as Au, Al, ZnO, TiO₂ etc.)

(f) optionally an extra electrode to match the energy level,

(g) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,

(h) a photoactive layer,

(i) optionally a smoothing layer,

(j) an anode (electrode),

(k) a substrate.

The PV device can also be processed on a fiber as described, forexample, in US20070079867 and US 20060013549.

Due to their excellent self-organising properties the materials or filmscomprising the compounds of the formula I can also be used alone ortogether with other materials in or as alignment layers in LCD or OLEDdevices, as described for example in US2003/0021913.

Various features and aspects of the present invention are illustratedfurther in the examples that follow. While these examples are presentedto show one skilled in the art how to operate within the scope of thisinvention, they are not to serve as a limitation on the scope of theinvention where such scope is only defined in the claims. Unlessotherwise indicated in the following examples and elsewhere in thespecification and claims, all parts and percentages are by weight,temperatures are in degrees centigrade and pressures are at or nearatmospheric.

EXAMPLES Example 1

a) 20 g of [88949-34-2] and 25.76 g of potassium carbonate are suspendedin 300 ml of dry dimethylformamide and the mixture is heated to 90° C.under nitrogen. Then 79 g of [1044598-79-9] are added drop wise. Thereaction mixture is then stirred for 6 h at 90° C. After cooling to roomtemperature ethylacetate is added and the mixture is washed with water.The organic phase is dried over magnesium sulfate and the solvent isevaporated. The product is purified by column chromatography over silicato obtain compound 1. ¹H-NMR data (ppm, CDCl₃): 8.33 2H d, 7.60 2H d,6.68 2H d×d, 4.03 4H d, 1.85-1.75 2H m, 1.45-1.15 48H m, 0.88 6H t, 0.866H t.

b) 26.30 g of compound 1 are dissolved in 300 ml of chloroform. Themixture is cooled to −10° C. and then 11.42 g of N-bromo-succinimid(NBS) are added and the mixture is stirred for 2 hours at −10° C. Thereaction mixture is washed with water, dried with magnesium sulfate andthe solvent is evaporated. The crude product is purified by columnchromatography over silica to obtain compound 2. ¹H-NMR data (ppm,CDCl₃): 8.35 1H d, 8.30 1H d, 7.62 1H d, 6.71 1H d×d, 6.62 1H d, 4.03 2Hd, 4.00 2H d, 1.87-1.75 2H m, 1.45-1.20 48H m, 0.88 6H t, 0.86 6H t.

c) 232 mg of compound 2, 58 mg of compound [1256165-36-2], 2 mg ofPd(OAc)₂ and 25 mg of 2-(di-tert-butylphosphino)-1-phenylindole areplaced into a reactor under Argon. Then 20 ml oxygen free THF are addedand the reaction mixture is heated to 50° C. Then 37 mg of lithiumhydroxide monohydrate are added and the reaction mixture is then heatedfor 2 hours at reflux temperature. The reaction mixture is poured onice/water and then extracted with chloroform. The organic solution isdried over MgSO₄ and evaporated. Compound 3 is then obtained aftercolumn chromatography of the crude product. ¹H-NMR data (ppm, CDCl₃):8.46 2H d, 8.36 2H d, 7.71 2H s, 7.62 2H s, 7.59 2H d, 6.89 2H d, 6.702H d, 4.13 4H d, 4.03 4H d, 1.96 2H broad s, 1.83 2H broad s, 1.45-1.1596H m, 0.89 12H t, 0.82 12H t.

Example 2

Two equivalents of compound 2 and 1 equivalent of compound [175361-81-6]are reacted according to the example 1 to obtain compound 4.

Example 3

Two equivalents of compound 2 and 1 equivalent of compound [239075-02-6]are reacted according to the example 1 to obtain compound 5.

Example 4

Two equivalents of compound 2 and 1 equivalent of compound [476004-84-9]are reacted according to the example 1 to obtain compound 6.

Example 5

Two equivalents of compound 2 and 1 equivalent of compound [849543-98-2]are reacted according to the example 1 to obtain compound 7.

Application Example 1 Bottom Gate Bottom Contact (BGBC) Field-EffectTransistor (FET)

Standard procedure for transistors on silicon substrates: Heavily dopedsilicon wafers (Si n−(425±40 μm) with a 230 nm thick thermally grownsilicon dioxide layer having on top of the silicon dioxide layer indiumtin oxide (15 nm)/gold (30 nm) contacts are used as substrates. Thesubstrates are prepared by standard cleaning in acetone and i-propanolfollowed by oxygen plasma treatment for 30 minutes and are thentransferred in a glove box and treated with octyltrichlorosilane (OTS)to achieve a hydrophobic monolayer.

Deposition of Semiconductor Film:

The semiconductor, compound 3, is dissolved in toluene in aconcentration of 0.75% by weight at elevated temperature and isspin-coated at 1500 rounds per minute (rpm) for 60 seconds onto thesilicon dioxide/silicon substrate. All electrical measurements areperformed under a nitrogen atmosphere in a glove box with a gate voltage(Vg) varying from 10 to −30 V and at a drain voltage (Vd) equal to 3 and30V for the transfer characterisation. For the output characterizationVd is varied from 0 to −30V at Vg=0, 10, 20, 30 V. The measuredmobilities represent the saturation mobilities at Vd=−30V.

The compound 3 has excellent solubility in organic solvents andexcellent film-forming properties. The FET of Application Example 1,where the semiconductor layer consists of compound 3, shows p-typecharacteristics with excellent processibility and reproducibility.

Application Example 2 Organic Bulk Heterojunction Solar Cell

The solar cell has the following structure: Al electrode/LiFlayer/organic layer, comprising compound 3 and1-[3-(methoxycarbonyl)propyl]-1-phenyl-[6.6]C₆₁3′H-cyclopropa[1,9][5,6]fullerene-C₆₀-lh-3′-butanoic acid 3′-phenylmethyl ester ([60]PCBM)/[poly(3,4-ethylenedioxy-thiophene) (PEDOT) inadmixture with poly(styrenesulfonic acid) (PSS)]/ITO electrode/glasssubstrate. The solar cells are made by spin coating a layer of thePEDOT-PSS on a pre-patterned ITO on glass substrate. Then a 1:2 mixtureof the compound of the present invention (1% by weight):[60]PCBM (asubstituted C₆₀ fullerene) is spin coated from chloroform. (organiclayer). LiF and Al are sublimed under high vacuum through a shadow-mask.

Solar Cell Performance:

The solar cell is measured under Aescusoft solar light simulator withhalogen light source. The current is estimated under AM1.5 conditionsusing the External Quantum Efficiency (EQE) graph.

The solar cell of Application Example 1, where the semiconductor layerconsists of compound 3 and [60]PCBM, shows OPV characteristics withexcellent processibility and reproducibility.

The invention claimed is:
 1. A compound of formula (I)

wherein p is 0, or 1, q is 0, or 1, A¹ and A² are independently of eachother a group of formula

A³, A⁴ and A⁵ are independently of each other a group of formula

a is 1 or 2; b is 0, 1 or 2; c is 0, 1 or 2; k is 0, 1, or 2; l is 1, 2,or 3; r is 0, or 1; z is 0, 1 or 2; R¹, R², R^(1′), R^(2′), R^(1″),R^(2″), R^(1*) and R^(2*) may be the same or different and are a C₁-C₁₀₀alkyl group which can optionally be substituted one or more times withC₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano,vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, a silyl group or a siloxanylgroup and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, —COO—,—CO— or —OCO; R³ is hydrogen, Ar¹ is

 and Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are independently of each other abivalent group of formula

X is —O—, —S—, —NR¹⁰—, —Si(R¹⁸)(R¹⁹)—, —Ge(R¹⁸)(R¹⁹)—, —C(R¹²)(R¹³)—,—C(═CR¹⁴R¹⁵),

R¹⁰ and R¹¹ are independently of each other hydrogen, C₁-C₁₈alkyl,C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl, R¹² and R¹³ areindependently of each other hydrogen, C₁-C₁₈alkyl, C₁-C₁₈haloalkyl,C₇-C₂₅arylalkyl, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl, or R¹² and R¹³together represent oxo,

or form a five or six membered ring, which is unsubstituted orsubstituted by C₁-C₁₈alkyl and/or C₁-C₁₈alkoxy; R¹⁴ and R¹⁵ areindependently of each other hydrogen, C₁-C₁₈alkyl, C₆-C₂₄aryl,C₂-C₂₀heteroaryl, —CN or COOR⁵⁰; R¹⁶ and R¹⁷ are independently of eachother hydrogen, halogen, C₁-C₂₅alkyl, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

R^(x) is a C₁-C₁₂alkyl group, or a tri(C₁-C₈alkyl)silyl group, R¹⁸ andR¹⁹ are independently of each other hydrogen, C₁-C₁₈alkyl,C₇-C₂₅arylalkyl, or a phenyl group, which optionally can be substitutedone to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, R²⁰ and R²¹ areindependently of each other hydrogen, C₁-C₂₅alkyl, C₂-C₂₅alkenyl,C₂-C₂₅alkyl which is interrupted by one or more —O— or —S—, COOR⁵⁰,cyano, C₁-C₁₈alkoxy, C₆-C₂₄aryl, C₇-C₂₅arylalkyl, halogen orC₂-C₂₀heteroaryl, or R²⁰ and R²¹ together represent alkylene oralkenylene which may be both bonded via oxygen and/or sulfur to the(hetero)aromatic residue and which may both have up to 4 carbon atoms,R³⁰ to R³⁷ are independently of each other hydrogen, C₁-C₂₅alkyl,C₂-C₂₅alkenyl, C₂-C₂₅alkyl which is interrupted by one or more —O— or—S—, COOR⁵⁰, cyano, C₁-C₂₅alkoxy, C₆-C₂₄aryl, C₇-C₂₅arylalkyl, halogenor C₂-C₂₀heteroaryl, R⁴⁰ and R⁴¹ are independently of each otherhydrogen, C₁-C₂₅alkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkyl which is interruptedby one or more —O— or —S—, COOR⁵⁰, cyano, C₁-C₁₈alkoxy, C₆-C₂₄aryl,C₇-C₂₅arylalkyl, halogen or C₂-C₂₀heteroaryl, R⁵⁰ is C₁-C₂₅alkyl,C₁-C₂₅haloalkyl, C₇-C₂₅arylalkyl, C₆-C₂₄aryl or C₂-C₂₀heteroaryl; R⁶⁰ toR⁶⁸ represent independently of each other H, halogen, cyano,C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, a C₄-C₁₈cycloalkyl group, aC₄-C₁₈cycloalkyl group, which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, C₇-C₂₅aralkyl, or C₇-C₂₅aralkyl, which issubstituted by G, R⁷⁰ and R⁷¹ are independently of each other hydrogen,C₁-C₂₅alkyl, or C₇-C₂₅aralkyl, or R⁷⁰ and R⁷¹ together representalkylene or alkenylene which may be both bonded via oxygen and/or sulfurto the thienyl residue and which may both have up to 25 carbon atoms, Dis —CO—, —COO—, —S—, —O—, —NR³⁹—, or —C(═O)NR³⁹—, E is C₁-C₈thioalkoxy,COO—C₁-C₁₈alkyl, C₁-C₈alkoxy, CN, —NR³⁹R^(39′), —CONR³⁹R^(39″), orhalogen, G is E, or C₁-C₁₈alkyl, R³⁹ and R^(39′) are independently ofeach other hydrogen, C₁-C₁₈alkyl, C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, orC₁-C₁₈alkanoyl, with the proviso that Ar⁵ is different from a group

if q is 0, p is 0, k is 0, r is 0, z is 0 and l is
 1. 2. The compoundaccording to claim 1 of formula (Ia), (Ib) or (Ic)


3. The compound according to claim 1, wherein R¹, R², R^(1′), R^(2′),R^(1″), R^(2″), R^(1*) and R^(2*) may be the same or different and areC₁-C₅₀alkyl, C₁-C₅₀haloalkyl, C₇-C₂₅arylalkyl.
 4. The compound accordingto claim 1, wherein A¹ and A² are independently of each other a group ofFormula

wherein a is 1, b is 0, or 1, c is 0, or 1, Ar² and Ar³ areindependently of each other a group of formula

R¹⁰ is a hydrogen, C₁-C₂₅alkyl or COO—C₁-C₂₅alkyl, R¹⁶ and R¹⁷ areindependently of each other hydrogen, halogen, C₁-C₂₅alkyl,C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

R^(X) is a C₁-C₁₂alkyl group, or a tri (C₁-C₈alkyl)silyl group, R²⁰ andR²¹ are independently of each other hydrogen, or C₁-C₂₅alkyl, R³⁰ to R³⁵are independently of each other hydrogen, or C₁-C₂₅alkyl, R⁴² and R⁴³are independently of each other C₁-C₂₅alkyl; and R³ is hydrogen.
 5. Thecompound according to claim 4, wherein A¹ and A² are independently ofeach other a group of formula

wherein a is 1, b is 0, or 1, c is 0, or 1, Ar² and A³ are independentlyof each other

and R³ is H.
 6. The compound according to claim 1, wherein A³, A⁴ and A⁵are independently of each other a group of formula

k is 0, 1, or 2; l is 1, 2, or 3; r is 0, or 1; z is 0, 1 or 2; Ar⁴,Ar⁵, Ar⁶ and Ar⁷ are independently of each other a group of formula

R¹⁰ is hydrogen, C₁-C₂₅alkyl or COO—C₁-C₂₅alkyl, R¹⁶ and R¹⁷ areindependently of each other hydrogen, halogen, C₁-C₂₅alkyl,C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

R^(X) is a C₁-C₂₅alkyl group, or a tri(C₁-C₈alkyl)silyl group, R²⁰ andR²¹ are independently of each other hydrogen, or C₁-C₂₅alkyl, R³⁰ to R³⁵are independently of each other hydrogen, or C₁-C₂₅alkyl, and R⁴² andR⁴³ are independently of each other C₁-C₂₅alkyl.
 7. The compoundaccording to claim 5, wherein A³, A⁴ and A⁵ are independently of eachother a group of formula

k and z are 0, or 1; l is 1, 2, or 3; r is 0; Ar⁴ and Ar⁷ are a group offormula

Ar⁵ is a group of formula

y is 1, 2 or 3, R¹⁰ is H, or C₁-C₂₅ alkyl, R¹⁶ and R¹⁷ are H, orC₁-C₂₅alkyl, and R³² and R³³ are H, or C₁-C₂₅alkoxy.
 8. The compoundaccording to claim 1 of formula (IIa), (IIb), (IIc), (IIIa), (IIIb) or(IIIc),

wherein b is 0, or 1, c is 0, or 1, A³, A⁴, Ar⁵ and Ar⁶ areindependently of each other a group of formula

y is 1, 2, or 3, Ar² and Ar³ are independently of each other

R¹, R², R^(1′), R^(2′), R^(1*)and R^(2*) are C₁-C₅₀alkyl,C₁-C₅₀haloalkyl, C₇-C₂₅arylalkyl R³ is H, R¹⁰ is H, or C₁-C₂₅alkyl, R¹⁶and R¹⁷ are H, or C₁-C₂₅alkyl, and R³² and R³³ are H, or C₁-C₂₅alkoxy.9. A compound of formula (A-1)-(A22), (B-1) or (B-2)


10. A semiconductor device comprising a compound of the formula I asdefined in claim
 1. 11. A semiconductor device according to claim 10 inthe form of a diode, a photodiode, a sensor, an organic field effecttransistor, a transistor for flexible displays, or a solar cell.
 12. Thecompound according to claim 2 wherein R¹, R², R^(1′), R^(2′), R^(1″),R^(2″), R^(1*) and R^(2*) may be the same or different and areC₁-C₅₀alkyl, C₁-C₅₀haloalkyl, C₇-C₂₅arylalkyl.
 13. The compoundaccording to claim 2, wherein A¹ and A² are independently of each othera group of formula

wherein a is 1, b is 0, or 1, c is 0, or 1, Ar² and Ar³ areindependently of each other a group of formula

R¹⁰ is hydrogen, C₁-C₂₅alkyl or COO—C₁-C₂₅alkyl, R¹⁶ and R¹⁷ areindependently of each other hydrogen, halogen, C₁-C₂₅alkyl,C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

R^(X) is a C₁-C₁₂alkyl group, or a tri(C₁-C₈alkyl)silyl group, R²⁰ andR²¹ are independently of each other hydrogen, or C₁-C₂₅alkyl, R³⁰ to R³⁵are independently of each other hydrogen, or C₁-C₂₅alkyl, R⁴² and R⁴³are independently of each other C₁-C₂₅alkyl; and R³ is hydrogen.
 14. Thecompound according to claim 12, wherein A¹ and A² are independently ofeach other a group of formula

wherein a is 1, b is 0, or 1, c is 0, or 1, Ar² and Ar³ areindependently of each other a group of formula

R¹⁰ is hydrogen, C₁-C₂₅alkyl or COO—C₁-C₂₅alkyl, R¹⁶ and R¹⁷ areindependently of each other hydrogen, halogen, C₁-C₂₅alkyl,C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

R^(X) is a C₁-C₂₅alkyl group, or a tri(C₁-C₈alkyl)silyl group, R²⁰ andR²¹ are independently of each other hydrogen, or C₁-C₂₅alkyl, R³⁰ to R³⁵are independently of each other hydrogen, or C₁-C₂₅alkyl, R⁴² and R⁴³are independently of each other C₁-C₂₅alkyl; and R³ is hydrogen.
 15. Thecompound according to claim 14, wherein A¹ and A² are independently ofeach other a group of formula

wherein a is 1, b is 0, or 1, c is 0, or 1, Ar² is,

and R³ is H.
 16. The compound according to claim 15, wherein A³, A⁴ andA⁵ are independently of each other a group of formula

k is 0, 1, or 2; l is 1, 2, or 3; r is 0, or 1; z is 0, 1 or 2; Ar⁴,Ar⁵, Ar⁶ and Ar⁷ are independently of each other a group of formula

R¹⁰ is hydrogen, C₁-C₂₅alkyl or COO—C₁-C₂₅alkyl, R¹⁶ and R¹⁷ areindependently of each other hydrogen, halogen, C₁-C₂₅alkyl,C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

R^(X) is a C₁-C₁₂alkyl group, or a tri(C₁-C₈alkyl)silyl group, R²⁰ andR²¹ are independently of each other hydrogen, or C₁-C₂₅alkyl, R³⁰ to R³⁵are independently of each other hydrogen, or C₁-C₂₅alkyl, and R⁴² andR⁴³ are independently of each other C₁-C₂₅alkyl.
 17. The compoundaccording to claim 15, wherein A³, A⁴, and A⁵ are independently of eachother a group of formula

k and z are 0, or 1; 1 is 1, 2, or 3; r is 0; Ar⁴ and Ar⁷ are a group offormula

Ar⁵ is a group of formula

y is 1, 2, or 3, R¹⁰ is H, or C₁-C₂₅alkyl, R¹⁶ and R¹⁷ are H, orC₁-C₂₅alkyl, and R³² and R³³ are H, or C₁-C₂₅alkoxy.
 18. The compoundaccording to claim 17 of formula (IIa), (IIb), (IIc), (IIIa), (IIIb) or(IIIc),

wherein b is 0, or 1, c is 0, or 1, A³, A⁴, Ar⁵ and Ar⁶ areindependently of each other a group of formula

y is 1, 2, or 3, Ar² and Ar³ are independently of each other

R¹, R², R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) and R^(2*) are selectedfrom hydrogen, C₁-C₅₀alkyl, C₁-C₅₀haloalkyl, C₇-C₂₅arylalkyl,C₂-C₅₀alkenyl, C₂-C₅₀haloalkenyl, allyl, C₅-C₁₂cycloalkyl, phenyl, ornaphthyl which can optionally be substituted one or more times withC₁-C₁₂alkyl or C₁-C₁₂alkoxy, —O—C₁-C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl and—COO—C₁-C₁₈alkyl, R³ is H, R¹⁰ is H, or C₁-C₂₅alkyl, R¹⁶ and R¹⁷ are H,or C₁-C₂₅alkyl, and R³² and R³³ are H, or C₁-C₂₅alkoxy.